Nickel(ii) complexes of a 3N ligand as a model for diketone cleaving unusual nickel(ii)-dioxygenase enzymes†‡,Dalton Transactions

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Nickel(ii) complexes of a 3N ligand as a model for diketone cleaving unusual nickel(ii)-dioxygenase enzymes†‡
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-02-13 00:00:00 , DOI: 10.1039/c7dt04739h
Ramamoorthy Ramasubramanian _{1,

2,

3,

4,

5} , Karunanithi Anandababu _{1,

2,

3,

4,

5} , Mukesh Kumar _{5,

6,

7,

8} , Ramasamy Mayilmurugan _{1,

2,

3,

4,

5}

Affiliation

Diketone substrate bound nickel(II) complexes of 2,6-bis(1-methylbenzimidazolyl)pyridine have been synthesized and characterized as relevant active site models for unusual diketone cleaving Ni(II)-dependent enzymes Ni–ARD and DKDO. The average Ni–N_py/benzim bond distances (2.050–2.107 Å) of model complexes are almost identical to the Ni–N_His bond distances of Ni^II–ARD (2.02–2.19 Å). The reaction of these adducts with dioxygen exhibited C–C cleavage with the rate of k_O₂, 5.24–73.71 × 10⁻³ M⁻¹ s⁻¹. The phenyl substituted adduct regioselectively elicits 52% of benzoic acid as the major product.

中文翻译：

3N配体的镍（ii）络合物作为二酮裂解不常见的镍（ii）-双加氧酶的模型† ‡

已合成了与二酮与基质结合的2,6-双（1-甲基苯并咪唑基）吡啶的镍（II）配合物，并将其表征为相关的活性位点模型，用于异常的二酮裂解Ni- II依赖性酶Ni-ARD和DKDO。模型配合物的平均Ni–N _{py /苯甲醛}键距（2.050–2.107Å）与Ni ^II– ARD的Ni–N _His键距几乎相同（2.02–2.19Å）。这些加合物与双氧的反应显示出C–C裂解，k _O_₂的速率为5.24–73.71×10 ^-3 M ^-1 s ^-1。苯基取代的加合物区域选择性地引发52％的苯甲酸作为主要产物。

更新日期：2018-02-13

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